EP0555010B1 - Verfahren zur Herstellung eines Silizium-Einkristalls - Google Patents

Verfahren zur Herstellung eines Silizium-Einkristalls Download PDF

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Publication number
EP0555010B1
EP0555010B1 EP93300615A EP93300615A EP0555010B1 EP 0555010 B1 EP0555010 B1 EP 0555010B1 EP 93300615 A EP93300615 A EP 93300615A EP 93300615 A EP93300615 A EP 93300615A EP 0555010 B1 EP0555010 B1 EP 0555010B1
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EP
European Patent Office
Prior art keywords
silicon
single crystal
grains
polycrystal
melt
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP93300615A
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English (en)
French (fr)
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EP0555010A1 (de
Inventor
Kiyotaka C/O Semiconductor Res.Inst. Takano
Izumi C/O Semiconductor Res.Inst. Fusegawa
Hirotoshi Semiconductor Res.Inst. Yamagishi
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Shin Etsu Handotai Co Ltd
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Shin Etsu Handotai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method

Definitions

  • the present invention relates to a process for producing a silicon single crystal and more particularly to a process for pulling up the silicon single crystal by the Czochralski method (referred to as a CZ method hereinafter).
  • a dopant such as phosphorus (P) or boron (B) is added to a silicon melt in a crucible after a raw silicon polycrystal is melted and the silicon single crystal is grown after the concentration of the dopant in the melt is controlled.
  • the segregation coefficient of the dopant is less than one (the segregation coefficient of phosphorus is 0.35 , the segregation coefficient of boron is 0.75)
  • the concentration of the dopant in the melt increases during growth of the silicon single crystal.
  • the resistivity of the resulting silicon single crystal rod decreases from the head to the tail of the silicon single crystal rod.
  • Silicon polycrystal ingot or a block-shaped silicon polycrystal has been employed as the raw silicon polycrystal in both the melt-reduced and melt-constant continuous charge methods. Since simply soaking the silicon polycrystal ingot in the melt cannot control the amount of silicon polycrystal ingot fed to the melt, it has been proposed that a heater for melting the silicon polycrystal ingot is provided in a chamber for growth of single crystal or that a chamber is separated into a chamber for growth of single crystal and a chamber for melting raw silicon polycrystal and a quartz piping connects the chamber for growth of single crystal to the chamber for melting raw silicon polycrystal.
  • the both cases are impractical since the systems of the cases are complicated and expensive.
  • the present inventors discovered that since the production of the grains of silicon polycrystal by the reaction on the fluidized bed contains a large amount of residual hydrogen in the grains of silicon polycrystal,when the grains of silicon polycrystal are dropped into the melt, the melt splashes during a continuous charge of the grains of silicon polycrystal. That is, since the grains of silicon polycrystal are instantly exposed to an ultra high temperature (melting point of silicon of 1420°C) when they dropped to the melt, the residual hydrogen in the grains of silicon polycrystal causes splashes of the melt. On the other hand, a dehydrogenation of the grains of silicon polycrystal by a high temperature heat treatment for preventing the splashing of the melt tends to make a growing silicon single crystal polycrystalline.
  • the isolation effect of a separating wall is relatively reduced and semimolten grains of silicon polycrystal rise to the surface of the melt in the internal crucible. That is, it is supposed that a probability that grains of silicon polycrystal in a solid state go around the bottom of the internal crucible and reach the silicon single crystal rod is increased. Thus, the silicon single crystal rod tends to be made polycrystalline.
  • EP-A-0450393 discloses the preparation of semiconductor-grade polysilicon in the form of free-flowing particles having a hydrogen content of less than 30 ppma. It is also disclosed that such particles are suitable for the advanced Czochralski pulling process.
  • EP-A-0363742 discloses another process for preparing a silicon having a reduced hydrogen content, i.e. less than 30 ppma.
  • the concentration by weight of residual hydrogen in the grains of silicon polycrystal is between 10 and 100 ppm.
  • the grains of silicon polycrystal are fed in a controlled amount to the silicon melt concurrently with growth of a silicon single crystal.
  • the process of this invention effectively prevents the silicon single crystal from becoming polycrystalline during growth.
  • the use of the given concentration of residual hydrogen prevents the emission of gaseous hydrogen at the moment the grains of silicon polycrystal drop into the silicon melt in the crucible to prevent a splash of the silicon melt even if they are exposed to an ultra high temperature (e.g. the melting point of silicon of 1420°C).
  • the grains of silicon polycrystal of the concentration of residual hydrogen more than 10 ppmwt and less than 100 ppmwt are employed as a raw material in a method of continuously charging an undoped silicon polycrystal in a process for producing the silicon single crystal, they prevent a splash of the silicon melt in the crucible and the silicon single crystal from being made polycrystalline since they are not an almost fully dehydrogenated silicon polycrystal.
  • the performance of the method of the continuous charge of the grains of silicon polycrystal is remarkably improved. This is decisively advantageous since the feed speed of the raw silicon polycrystal must be increased correspondingly to an increase in the weight of the silicon single crystal when a silicon single crystal having a large diameter is grown.
  • both the melt-reduced continuous charge method and the melt-constant continuous charge method employ grains of silicon polycrystal of which a concentration of residual hydrogen of is more than 10 ppmwt and less than 100 ppmwt as an undoped raw silicon polycrystal in pulling up the silicon single crystal.
  • the grains of silicon polycrystal are produced, e.g., by the following steps:
  • Grains of silicon polycrystal of 50 g ⁇ 0.01g (a sample) was fastened to the center of the interior of a combustion tube by means of glass wool.
  • the combustion tube was placed in a furnace at a temperature of 100°C or less.
  • Gaseous argon of 10 ml/min purged an original gas (especially nitrogen) out of the combustion tube for 15 min.
  • the gaseous argon passed through a thermal conductivity sensor electrically and pneumatically balanced and was discarded from the combustion tube.
  • the sample was heat treated at 225°C for 30 min to eliminate a gas adsorbed on the surface of the sample. During this time, no changes in a signal from the thermal conductivity sensor were integrated.
  • a furnace temperature was increased at a rate of 20°C/min to 1200°C and subsequently maintained at 1200°C until gaseous argon fully purged hydrogen out of the sample.
  • a full dehydrogenation of the sample required approximately 3hr.
  • signals from the thermal conductivity sensor were integrated.
  • a cylindrical pump injected pure hydrogen of 0.1-10 ml into gaseous argon for a few hours. This injection simulates hydrogen from real sample in gaseous argon as a carrier.
  • the system was calibrated within the range of a concentration of hydrogen of 4-1000 ppma in a silicon polycrystal.
  • the calibration is linear within the range of this concentration and has a precision of ⁇ 5-6% in relative standard deviation.
  • a casing was made of a wafer in the form of a polishing wafer (PW) and the infrared absorbance of the case gave a background for the determination of the infrared absorbance of the grains of silicon polycrystal. Subsequently, a few number of grains of silicon polycrystal previously classified by grain sizes were placed in the casing. An infrared radiation was subsequently transmitted to the casing holding the grains of silicon polycrystal for the determination of the infrared absorbance of the grains. The infrared absorption (reflection) spectra of the grains of silicon polycrystal were determined.
  • the FT-IR is a technique of using a spectroscope to analyze the infrared absorption or reflection spectra of a sample and gives a high-speed, high-sensitive, noncontact and nondestructive evaluator.
  • An optical system of a FT-IR apparatus has a structure in which an infrared beam from a source of light is collimated and then enters a Michelson interferometer.
  • the FT-IR apparatus transmits an infrared radiation from the Michelson interferometer to the sample and senses an interfered infrared radiation penetrating through or reflected by the sample.
  • the FT-IR apparatus determines an interfered waveform of the sensed interfered infrared radiation as a function of an optical path difference caused by the operation of a movable mirror of the Michelson interferometer, applied Fourier transformation on the interfered waveform of the collimated infrared radiation penetrating through or reflected by the sample with an interfered waveform of a reference infrared radiation neither penetrating through nor reflected by the sample, and produces the infrared absorption or reflection spectra of the sample from a difference between the two interfered waveforms.
  • the peak intensity of the infrared absorption spectra was near 2000/cm, the peak intensity was selected for the determination of the concentration of the residual hydrogen.
  • FIG.1 shows computed feed speeds of the grains of silicon polycrystal of a case where an N type silicon single crystal is pulled up by the melt-reduced continuous charge method, a case where a P type silicon single crystal is pulled up by the melt-reduced continuous charge method and a case where a silicon single crystal is pulled up by the melt-constant continuous charge method.
  • the crystal growth speed SE was computed in a unit of 1.0 mm/min.
  • the feed speeds of the grains of silicon polycrystal in the melt-reduced continuous charge method were computed on a condition that the resistivity through the silicon single crystal rod was flat lengthwise.
  • FIG.2 shows relations of concentrations of the residual hydrogen and rates of monocrystallinity of resulting silicon crystal rods.
  • the rates of monocrystallinity of the silicon crystal rods were computed as follows: Lots of grains of silicon polycrystal having different concentrations of the residual hydrogen were prepared. Multiple batches of silicon single crystal growth were performed from each lot of the grains of silicon polycrystal on the same condition of crystal growth by the same silicon single crystal puller. The number of resulting silicon single crystals having no polycrystallization devided by the number of growth batches from each lot of grains of silicon polycrystal gave the rates of monocrystallinity of the silicon single crystals.
  • the test resulted in a rate of monocrystallinity of 80% where the concentration of the residual hydrogen is more than 6 ppmwt and less than 125 ppmwt and a rate of monocrystallinity of 90% or more where the concentration of the residual hydrogen is more than 10 ppmwt and less than 100 ppmwt.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (2)

  1. Verfahren zur Herstellung eines Silicium-Einkristalls, umfassend die Zugabe von Körnern eines Silicium-Polykristalls zu einer Siliciumschmelze in einem Tiegel und Ziehen eines Silicium-Einkristalls aus der Siliciumschmelze, dadurch gekennzeichnet, daß die Gewichtskonzentration an restlichem Wasserstoff in den Körnern des Silicium-Polykristalls zwischen 10 und 100 ppm beträgt.
  2. Verfahren nach Anspruch 1, worin die Körner des Silicium-Polykristalls in kontrollierter Menge, übereinstimmend mit dem Wachstum des Silicium-Einkristalls, der Siliciumschmelze zugeführt werden.
EP93300615A 1992-01-30 1993-01-28 Verfahren zur Herstellung eines Silizium-Einkristalls Expired - Lifetime EP0555010B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4038394A JP2506525B2 (ja) 1992-01-30 1992-01-30 シリコン単結晶の製造方法
JP38394/92 1992-01-30

Publications (2)

Publication Number Publication Date
EP0555010A1 EP0555010A1 (de) 1993-08-11
EP0555010B1 true EP0555010B1 (de) 1995-12-20

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EP93300615A Expired - Lifetime EP0555010B1 (de) 1992-01-30 1993-01-28 Verfahren zur Herstellung eines Silizium-Einkristalls

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US (1) US5340434A (de)
EP (1) EP0555010B1 (de)
JP (1) JP2506525B2 (de)
DE (1) DE69301035T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5588993A (en) * 1995-07-25 1996-12-31 Memc Electronic Materials, Inc. Method for preparing molten silicon melt from polycrystalline silicon charge
US5814148A (en) * 1996-02-01 1998-09-29 Memc Electronic Materials, Inc. Method for preparing molten silicon melt from polycrystalline silicon charge
US5919303A (en) * 1997-10-16 1999-07-06 Memc Electronic Materials, Inc. Process for preparing a silicon melt from a polysilicon charge
US6284040B1 (en) * 1999-01-13 2001-09-04 Memc Electronic Materials, Inc. Process of stacking and melting polycrystalline silicon for high quality single crystal production
JP2006315869A (ja) * 2005-05-10 2006-11-24 Sumco Corp 窒素ドープシリコン単結晶の製造方法
JP4604889B2 (ja) * 2005-05-25 2011-01-05 株式会社Ｓｕｍｃｏ シリコンウェーハの製造方法、並びにシリコン単結晶育成方法
DE102011002598B4 (de) * 2011-01-12 2016-10-06 Solarworld Innovations Gmbh Verfahren zur Herstellung eines Silizium-Ingots
DE102015106979B4 (de) * 2015-05-05 2023-01-12 Infineon Technologies Austria Ag Halbleiterwafer und Verfahren zum Herstellen von Halbleitervorrichtungen in einem Halbleiterwafer
WO2017062949A1 (en) * 2015-10-10 2017-04-13 Sunedison, Inc. System and method for degassing granular polysilicon

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1306407C (en) * 1987-06-08 1992-08-18 Michio Kida Apparatus for growing crystals of semiconductor materials
JPH0633218B2 (ja) * 1987-12-08 1994-05-02 日本鋼管株式会社 シリコン単結晶の製造装置
JPH01282194A (ja) * 1988-01-19 1989-11-14 Osaka Titanium Co Ltd 単結晶製造方法
US5037503A (en) * 1988-05-31 1991-08-06 Osaka Titanium Co., Ltd. Method for growing silicon single crystal
CA1340189C (en) * 1988-10-11 1998-12-15 Albemarle Corporation Polysilicon with diminished hydrogen content
JPH0676274B2 (ja) * 1988-11-11 1994-09-28 東芝セラミックス株式会社 シリコン単結晶の製造装置
DE68908872T2 (de) * 1989-02-03 1994-02-10 Mitsubishi Metal Corp Verfahren zum Ziehen von Einkristallen.
JP2672667B2 (ja) * 1989-08-28 1997-11-05 株式会社東芝 半導体単結晶の引上方法及びその装置
CA2038175A1 (en) * 1990-04-02 1991-10-03 Albemarle Corporation Polysilicon and process therefor
DE4106589C2 (de) * 1991-03-01 1997-04-24 Wacker Siltronic Halbleitermat Kontinuierliches Nachchargierverfahren mit flüssigem Silicium beim Tiegelziehen nach Czochralski

Also Published As

Publication number Publication date
DE69301035D1 (de) 1996-02-01
JP2506525B2 (ja) 1996-06-12
EP0555010A1 (de) 1993-08-11
DE69301035T2 (de) 1996-05-02
US5340434A (en) 1994-08-23
JPH05208889A (ja) 1993-08-20

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